Quaternary ammonium salts of high molecular weight acids



Patented July 20, 1931 UNITED STATES QUATERNARY AMIMONIUM SALTS OF HIGHMOLECULAR WEIGHT ACIDS,

Melvin De Groote, St. Louis, Mo., assignor to Tretolite Company, WebsterGroves, Mo., a 1

corporation of Missouri No Drawing. Application August 21, 1936, SerialNo. 97,221

15 Claims.

This invention relates to a novel composition of matter, and moreparticularly, to certain quaternary ammonium salts derived from acids ofhigh molecular weight and of the kind hereinafter described. Suchmaterials may be employed as wetting, washing, frothing, emulsifying,dispersing, softening, leveling, and plasticizing agents, and they alsomay be employed as assistants in the textile industry and various otherindustries.

It is well known that various high molecular weight acids, and moreparticularly, their salts, such as ammonium, potassium, sodium salts,etc., are the kind which exhibit surface-active properties. They give atypical colloidal sol in water or in hydrophobe solvents, in which theyhappen to be miscible, depending upon the specific agents selected.Examples of such materials include the following: Salts of higher fattyacids, resinates, rosinates, naphthenates, sulfoabietenes and the like,petroleum sulfonates of both the oil-soluble and oil-insoluble type,sulfated and sulfonated higher alcohols, substituted aromatic sulfonicacids, alkylated polycyclic sulfonic acids, cycloaromatic sulfonicacids, sulfated fatty acids, sulfonated fatty acids, the variouscogeners which accompany the sulfo or sulfated fatty acids or sulfonatedfatty acids obtained in sulfation or sulfonation processes, and areproduced by the hydrolysis of sulfo-fatty acids, followed, in someinstances, by condensation; fatty acids of the kind obtained byoxidation, particularly the oxidation of ricinoleic acid, i. e., blownoil, or blown oil fatty acids, fatty acid esters in which asulfoaromatic or sulfo-aliphatic residue has replaced the carboxylichydrogen; sulfonated fatty amides, sulfo-amides, in which a sulfonatedor sulfated alkyl group, or sulfonated or sulfated aryl group hasreplaced an amino hydrogen in the fatty amide residue; materials of thekind in which the hydroxyl of a fatty acid or of a glyceride hascombined with a polybasic carboxy acid, such as phthalated, oxalated,succinated, or maleated esters of ricinoleic acid, triricinolein,monoricinolein, di-ricinolein, mono-olein, di-olein, mono-stearin,di-stearin, mono-naphthenine, etc. Sulfo-aromatic fatty acids of theTwitchell reagent type, such as sulfo-naphthalene stearic acid,sulfo-benzene stearic acid, sulfo-phenol stearic acid, etc. representadditional examples. In the case that a maleic acid residue is present,it may, of course, be treated with a bisulfite, so as to be convertedinto a sulfo-succinic acid residue. In some instances, two moles of adibasic carboxy acid, for example, such as oxalic acid, may combine withtwo moles of triricinolein. Generally speaking, the properties areexhibited by materials having at least 8 carbon atoms in the molecule,and not over 120, as in the case of materials where two moles ofdi-ricinolein have been combined by mean-s of a dibasic acid, aspreviously pointed out. All these materials referred to are' well knowncompositions of matter, and the method of manufacturing the same is wellknown. They have been used in a variety of industries. Some reagentsfind application in a number of industries, whereas, other reagents arelimited to employment, perhaps, in one or two industries,

or even employment for a single purpose in a 15 particular industry.

It is to be noted that all the chemical compounds above referred to arecharacterized by the presence of an acid radical, which is either acarboxy acid radical, a sulfonic acid radical, or an acid sulfateradical, as in the case of fatty acid sulfates or alcohol sulfates. Theacids themselves may be characterized by the formula T.X.OH, in which Tis a high molecular weight residue consisting principally of carbonatoms and hydrogen atoms, and X.OH is the acid radi cal in which X is COor S02 or S03. In-some instances T is a hydrocarbon residue without anyother concomitant atoms or radicals being present, for instance, in thecase of propylated naphthalene sulfonic acid, or in the case of oleicacid, or in the case of petroleum sulfonic acid. In other instances,there may be a hydroxyl group attached to T, as in the caseofderivatives of ricinoleic acid, or derivatives of alkylated naphtholsulfonic acids. In other instances, T may contain a halogen atom, suchas in the case of chlorinated or brominated oleic acid, alkylatedchlornaphthalene sulfonic acid, etc. In still other instances, T mayhave an acid group attached thereto, as in the case of phthalated castoroil, oxylated ricinoleic acid, sulfo-naphthalene stearic acid, etc. Ineach case, however, T is a high molecular weight hydrocarbon residue orits til BaN[ (OH) nD].C1,

in which the various characters have their previous significance. Ifsuch material is dissolved in alcohol and reacted with an alcoholicsolution -of the sodium salt of acids of the kind previously described,there occurs a precipitation of sodium chloride with the formation ofthe corresponding salt, which may be indicated by the formula BaNE (OH)nD] .O.X.T.

in which the various characters have their previous significance. Thematerials so obtained from the high molecular weight surface-activeacids are much more efiective for various industrial purposes than thecorresponding metallic salts or corresponding simpler amine salts. Ihave also found that such materials are very effective softening agents,cleansing agents, detergent agents, emulsifying agents, wetting agents,and

leveling agents, and that they can be employed as auxiliary agents forthe same purpose. I do not contend that any single one of. the saidmaterials will serve for all of the purposes mentioned, but it isbelieved that no particular difficulty is involved in their application.Each one of the said materials or products is derived from a highmolecular weight surface-active acid, whose application in variousindustries in the form of simple metallic salts is well known. Insubstantially all instances, it will be found that reagents of the kinddescribed in which one employs the alkylated alkylol oralkylol-oxy-alkylol quaternary ammonium compounds, instead of thesimpler compounds, will result in a more effective compound for theparticular purpose for which the product is employed, or a compoundwhich will accomplish the same result at a lower cost.

It is to be noted that the high molecular weight surface-active acids ortheirsimpler salts may be described as being polar" compounds, in thesense that the word polar was used by Harkins in about 1917. The meaningof the word "polar" in this sense is intended to indicate that into thehydrophobe group or body there has been introduced a hydrophile group,such as a carboxyl group, or a sulfate group, or a sulfonic acid group,which tends to make the material dissolve in water or to spread out onwater, or to be wetted by water. Such polarity tends to make thematerials orient at interfaces. It is to be noted that the quaternaryammonium bases themselves, if they be of the kind described, exhibitthis same polar property, due to the presence of the hydrocarbonresidue, indicated by B, as contributing the hydrophobe portion, and dueto the nitrogen atom and the alkylol or alkylol-oxy-alkylol residueintroducing' the hydrophile residue. Indeed, in some instances, suchquaternary ammonium bases or simple salts, even in their simplest form,such as the chlorides, may show marked surface-active properties andproduce a colloidal sol of the kind comparable to that produced by highmolecular weight surface-active acids of the kind previously described.Briefly stated, then, such materials of the kind herein contemplated arecharacterized by the fact that one might consider both the anion and thecation as being polar, when considered as an integral part, and withoutconsideration to the natural polar relationship to each other. Therelationship is comparable to a compound in which both the anion andcation have hydrophobe and hydrophile components bound covalently,whereas, the anion and cation per se are bound electrovalently.

The quaternary ammonium compounds employed to produce the desired saltsmay be prepared in various manners. Glycerol may be converted bycustomary procedure into the chlorhydrin, or may be converted intoglycidol. Similarly, a glycol, such as ethylene glycol, may be convertedinto the corresponding chlorhydrin. Instead of the chlorhydrin one mayemploy the alkylene oxide. It is to be noted that reactions involvingglycidol or the alkylene oxides result in the formation of thequaternary base and not in the formation of the chloride. Naturally,such a quaternary base may be used directly to neutralize a highmolecular weight surface-active acid of the kind previously described.Polyhydric alcohols can be converted into ether alcohols, such asdi-glycerol ether or di-ethylene glycol ether. Such polyhydric alcoholethers can be converted into chlorhydrins in the same manner thatglycerol or ethylene glycol can be converted into a chlorhydrin. Suchchlorhydrins are entirely satisfactory for reaction with tertiary aminesto produce a suitable quaternary ammonium compound. For purpose ofillustration, the following examples are presented:

CHQOH CH2.0H

CHaCl Reactions need not be limited to the simpler tertiary amines, butone may select a secondary amine, such as diamyl-amine, and react itwith glycerol chlorhydrin, for example, to produce 1- diamyl aminopropane-2,3-diol (l-diamyl amino 2-hydroxy normal propanol). Suchproduct is in reality a substituted tertiary amine and may be indicatedby the formula:

Such a tertiary amine may be reacted further with another mole of thechlorhydrin derived from glycerol, ethylene glycol, or in fact, higherglycols, such as propylene glycol, butylene glycol, hydroxylated glycol,amylene glycol, non-amethylene glycol, decamethylene glycol, etc., or itmay be reacted with the alkylene oxides, such as ethylene oxide,propylene oxide, butylene oxide, amylene oxide, in the presence ofwater, etc.

Two molecules of glycerol mono-chlorhydrin can be reacted with one moleof mono-amylamine to yield a product of the following type:

This product can also be considered a tertiary amine, andmay be reactedin the manner previously described in regard to l-diamyl aminopropane-2,3-diol. Thus, in the reactions previously described, it hasbeen indicated that a primary amine can be reacted with two moles of asuitable chlorhydrin or its functional derivative, such'as'twomoles ofan alkylene oxide to give a product of the kind indicated immediatelyabove. However, instead of using mono-amylamine, one can employ anaralkyl amine, such as benzylamine, or a cyclic amine, such ascyclohexylamine, or their homologues. Piperidine is also satisfactoryfor reaction with a chlorhydrin to produce a tertiary amine.Incidentally, pyridine or its homologues are satisfactory as tertiaryalkyl amines for reactions of the kind described. For purposes ofclassification, pyridine and its homologues will be considered astrialkylated amines in which the Cal-I5 radical or the like isequivalent to three alkyl radicals. Such tertiary amines are reactedwith halohydrins of the kind described to form the quaternary ammoniumcompound.

It has been pointed out that the various reactions above referred to mayresult in the formation of a quaternary ammonium compound in the form ofa chloride. Such chloride can, of course, be reacted with a salt of thehigh molecular weight surface-active acid in a non-aqueous" solvent, sothat an inorganic chloride, such as sodium chloride, potassium chloride,or ammonium chloride is precipitated with the formation of thequaternaryammonium salt of the high molecular weight surface-active acid. On theother hand, it is simpler, as a rule, to convert the quaternary ammoniumchloride into the corresponding base by treatment-with an excess ofconcentrated caustic soda or caustic potash, so as to yield the baseitself and to employ the base for neutralization.

My preferred reagent is prepared by employing tri-amylamine or pyridineas the tertiary base and using glycidol for the reaction in which thequaternary ammonium compound is produced. 1,000 lbs. of tri-amylamine orthe equivalent amount of pyridine are reacted with 350 lbs. of glycidolin presence of about 75 lbs. of water, until a complete reaction hastaken place. The tri-amyl propane diol ammonium hydroxide orcorresponding pyridinium hydroxide, so produced, is used to neutralizevarious materials of the kind previously described, and particularlymaterials derived by the sulfation of castor oil, or by the sulfonationof oleic' acid, inpresence of a molecular amount of naphthalene, so asto produce sulfo-naphthaiene stearic acid, or for the neutralization ofpropylated or amylated naphthalene sulfonic acids, or for theneutralization of oxalated, phthalated, succinated or maleatedtri-ricinolein." I, have found that if the material is used for theneutralization of products obtained by the sulfation of castor oil, thatone obtains a new kind of Turkey red oil having unusual properties as adye bath assistant and as a wetting agent or leveling agent in thetextile industry. I have found that if mahogany acids of the kindderived in the refining of petroleum, as in the manufacture of white oilor medicinal oil, are neutralized with the above product, that oneobtains materials of unusual value in various processes involvingemulsification, such as the production of cutting oils for use inconnection with lathes and the like. I have found that if sulfo-aromaticfatty acids of the kind previously referred to are neutralized with thismaterial, that one obtains an emulsifying agent of unusual effectivenessfor producing oilin-water emulsions. I have found that if monophthalatedor di-phthalated ricinolein is neutralized with the above material, thatone obtains a plasticizer of unusual value in the manufacture of variousplastics, or in the manufacture of varnishes or lacquers derived fromresinous materials or cellulose bodies. I have found that all thevarious materials and all the various types previously mentioned areeffective in the resolution of oil field emulsions. In each instancewhere the high molecular weight surface-active fatty acids or itssimpler salts are employed in a particular industry, one can invariablyfind applica- "tion of the new quaternary ammonium compounds, so as toobtain increased efliciency or reduced cost.

For purpose of simplicity, the early discussion 3 in the presentinstance has been limited to products derived from the simplestquaternary compounds, such as indicated by the formulas B3N[(OH)1|.D].C1or B3N[(OH1;D].OH. It has been previously indicated that a secondaryamine irived from a glycerol ether, or from a glycol ether, the residuenot only would contain one 'or more hydroxyl radicals, but might alsocon tain an oxygen atom, due to the ether group. In such instances, the(OH) nD group might be designated as an alkylol-oxy-alkylol group.

For reasons just indicated, the quaternary ammonium compound maybeindicated as being of the type BmN[(0H)nD]1 n'-OH, in which the variouscharacters have their previous significance, 'with the qualificationthat B is preferably an alkyl radical having at least two carbon atoms,and m and m represent the numerals 'i, 2 or 3, and m and m' total 4. Itis possible that the radical D(OH)1:, where it appears more than onetime (in other words, where m has the value of 2 or 3) may #bedissimilar. It has been previously pointed out that any suitabletertiary amine may serve, such as tertiary propyl amine, tertiary butylamine, tertiary amyl amine, tertiary hexylamine, etc. Mixed alkylamines, such as tertiary amines, in which the alkyl groups aredissimilar, may be employed. It has been previously indicated how thecorresponding primary or secondary amines may be converted into tertiaryamines having at least one alkyl group or the like. Such amines may beemployed for reaction with halohydrins. It is also interesting astri-amylamine, or two moles of pyridine, that one obtains correspondingdiammonium salts, which are also valuable for neutralization of the highmolecular weight surface-active materials of the kind herein described.

The properties of the acids herein described which indicates theirsurface activity are well known. They are apt to produce a colloidalsol, particularly if dispersed in water. They tend to adsorb atinterfaces; they tend to produce froths or foams; they tend to produceemulsions; they tend to lower the surface tension of the solvent inwhich they are dissolved; they tend to dissolve in, be wetted by, orspread out on water. In some instances, these properties in regard towater are best observed by dissolving the material in alcohol and addingthe alcohol extract to a larger volume of water. The materials tend tohave a high molecular weight, etc. It is not necessary that each of theselected acids exhibit the various surface-active characteristics to theoptimum degree, but all of these materials exhibit one or more of theenumerated characteristics surface-active properties to a-greater orlesser degree, or else, some other obvious surface-active property. Allthese materials are of the kind which are conventionally understoodto'be surface-active, or have surface-active properties.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent, is:

1. A new composition of matter, consisting of a quaternary ammonium saltof a high molecular weight surface-active acid of the kind in which thesubstituted ammonium radical is characterized by the presence of atleast one hydrocarbon radical, and at least one radical selected fromthe class consisting of alkylol-oxy-alkylol radicals and alkylolradicals.

2. A new composition of matter, consisting of a quaternary ammonium saltof a high molecular weight surface-active acid of the kind in which thesubstituted ammonium radical is characterized by the presence of atleast one aralkyl radical, and at least one radical selected from theclass consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

3. A new composition of matter, consisting of a quaternary ammonium saltof a high molecular weight surface-active acid of the kind in which thesubstituted ammonium radical is characterized by the presence of atleast one cyclohexyl radical, and at least one radical selected from theclass consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

4. A new composition of matter, consisting of a quaternary ammonium saltof a high molecular weight surface-active acid of the kind in which thesubstituted ammonium radical is characterized by the presence of atleast one alkyl radical, and at least one radical selected from theclass consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

5. A'new composition of matter, consisting of a quarternary ammoniumsalt of a high molecular weight surface-active acid of the kind in whichthe substituted ammonium radical is characterized. by the presence of atleast one alkyl radical and at least one alkylol radical.

6. A new composition of matter, consisting of a quaternary ammonium saltof a high molecular weight surface-active acid of the kind in which thesubstituted ammonium radical is characterized by the presence of atleast one alkyl radical, said alkyl radical having at least two carbonatoms, and at least one alkylol radical.

'7. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and nothaving more than six carbon atoms; m and m are the numerals 1, 2 or 3,and m and m total 4; [(OH)nD] is an alkylol group, n denotes the numeral1, 2 or 3, and O.X.T represents an oil-soluble petroleum sulfonic acidradical.

9. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and nothaving more than six carbon atoms; m and m are the numerals 1, 2 or 3,and m and m total 4; [(OHMD] is an alkylol group, n denotes the numeral1, 2 or 3, and O.X.T represents an alkylated naphthalene sulfonic acidradical.

10. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and nothaving more than six carbon atoms; m and m are the numerals 1, 2 or 3,and m and m total 4; [(OH) 1D] is an alkylol group, n denotes thenumeral 1, 2 or 3, and O.X.T represents an acid radical derived byesterfication of a hydroxylated fatty body with a dibasic carboxy acid.

11. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and nothaving more than six carbon atoms; m and m are the numerals 1, 2 or 3,and m and m total 4; [(H)1.D] is ar. alkylol group, n denotes thenumeral 1, 2 or 3, and O.X.T represents an acid radical derived byesterification of triricinolein with a dibasic carboxy acid.

12. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and nothaving more than six carbon atoms; m and m are the numerals 1, 2 or 3,and m and m total 4; [(OHMD] is an alkylol group; n denotes the numeral1, 2 or 3, and O.X.T represents an acid radical derived byesterification of triricinolein with phthalic acid.

13. A new composition of matter indicated by the type formula:

in which B is an amyl radical; m and m are the numerals 1, 2 or 3, and mand m total 4; HOHMD] is an aikylol group; n denotes the numeral 1, 2 or3, and O.X.T represents an acid radical derived by esterification oftriricinolein with phthalic acid.

14. A new composition of matter indicated by the type formula:

in which Bis an amyl radical; m is the numeral 3 a and m is the numeral1; [(OH) "D1 is an alkylol group; n denotes the numeral 1, 2 or 3, andO.X.T

represents an acid radical derived by esterification of triricinoleinwith phthalic acid.

15. A new composition of matter indicated by the type formula:

in which B is an amyl radical; m is the numeral 3 and m is the numeral1; [(OH)nD] is the C3H5 (OH)2 radical; n denotes the numeral 1, 2 or 3,and O.X.'I represents an acid radical derived by esterification oftriricinoiein with phthalic acid.

MELVIN DE GROO'IE.

